Modulating stereoselectivity and catalytic efficiency of carbenoid reactions catalysed by self-sufficient P450s

Self-sufficient P450s are versatile biocatalysts. Among six self-sufficient P450 backbones, two variants from Tepidiphilus thermophilus exhibited a high TOF value of 1.5 min-1 (P450TT-C385S) and excellent diastereoselectivity of deE = 95.4% (P450TT-C385H). Molecular simulation was performed to reveal the different catalytic mechanisms among the self-sufficient P450 backbones. This work could provide useful information for exploring challenging unnatural reactions. Exploring the catalytic performance in the carbenoid-model-reaction of six self-sufficient P450s belonging to different families, and revealing their differences using molecular simulation.